CN103787336B - The method producing high purity granular silicon - Google Patents
The method producing high purity granular silicon Download PDFInfo
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- CN103787336B CN103787336B CN201410031137.3A CN201410031137A CN103787336B CN 103787336 B CN103787336 B CN 103787336B CN 201410031137 A CN201410031137 A CN 201410031137A CN 103787336 B CN103787336 B CN 103787336B
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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- B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
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- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/087—Heating or cooling the reactor
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- C01B33/00—Silicon; Compounds thereof
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- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
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Abstract
The invention discloses a kind of method producing high purity granular silicon, be reactor and the division of method of 200910149144.2 production high purity granular silicons.The method includes: a. forms high purity granular silicon bed；B. heating high purity granular silicon bed so that it is temperature is 100 DEG C-1400 DEG C；C. granular silicon in high purity granular silicon bed is made to be in relative motion state；D. being passed through auxiliary gas and unstrpped gas, produced reaction end gas is discharged；E. the high purity granular silicon obtained production is collected or is transported to next technique unit.The present invention is used in the high purity granular silicon bed of the dense accumulation of kinestate, avoid the bonding between granular silicon, reduce reactor volume, and by the high-purity powder silicon in the high purity granular silicon bed capture reaction tail gas of dense accumulation as seed, the waste heat also utilizing reaction end gas is supplementary granular silicon heating, it is achieved that ultra-large type, efficient, energy-conservation, continuous, low-cost production high purity granular silicon.
Description
Technical field
The present invention relates to HIGH-PURITY SILICON production technology, particularly relate to a kind of high purity granular silicon that produces
Method, is reactor and the division of method of 200910149144.2 production high purity granular silicons.
Background technology
Past HIGH-PURITY SILICON material is mainly used for producing semiconductor components and devices, along with quasiconductor collection
Becoming the development of circuit engineering, circuit level is more and more higher, although the application of electronic device is more
Come the widest, but the consumption of HIGH-PURITY SILICON does not has big increase.Owing to HIGH-PURITY SILICON still produces
The important source material of solar-energy photo-voltaic cell, and recently as the development of solar photovoltaic industry,
The most increasing to the demand of HIGH-PURITY SILICON, its demand has exceeded the consumption of semiconductor industry
And with rapid growth;On the other hand, photovoltaic industry belongs to the industry that profit margin is little,
Requiring that the production cost of HIGH-PURITY SILICON material is low, this proposes the biggest to traditional production method
Challenge.
Traditional method producing high purity polycrystalline silicon has Siemens Method and fluidized bed process.
Siemens Method is: the high-purity silicon-containing gas such as trichlorosilane (SiHCl after purifying3) or silicon
Alkane (SiH4) mix with hydrogen after be passed through in reactor, electrically heated silicon mandrel surface occur heat
Decomposition reaction, HIGH-PURITY SILICON is constantly deposited on red-hot silicon mandrel surface, is allowed to constantly increase slightly,
Reacted gas then returns to exhaust treatment system and carries out separating treatment and cycling and reutilization.
After silicon plug grows into certain diameter, it is necessary for terminating reaction, changes silicon plug the most again
Carry out next round reaction.This technique is intermittent operation, and power consumption is high, the most often gives birth to
Producing one kilogram of HIGH-PURITY SILICON needs power consumption 150kwh (kilowatt hour) left and right the highest.In addition this technique
There is also the shortcomings such as conversion efficiency is low.Therefore, Siemens Method produces HIGH-PURITY SILICON and yields poorly, and becomes
This height, it is impossible to meet growing industrial needs.
Fluidized bed process is: formed in the reactor of heating as " seed " by high purity granular silicon
Fluidized state, then introduces high-purity silicon-containing gas, so just sends out at heated the surface of the seed
Heat decomposition reaction, draws shape silicon the longest more big so that high-purity to such an extent as to cannot be floated and fall
Enter in collecting box.Owing to fluidized bed process utilizing substantial amounts of high purity granular silicon be " seed ", whole
Individual surface area has a larger increase relative to Siemens Method, and therefore reaction efficiency and conversion efficiency are all
Relatively Siemens Method improves a lot, and power consumption reduces the most therewith.
It has been investigated that traditional fluidized bed process produces, HIGH-PURITY SILICON existence is following mainly asks inventor
Topic:
1, high-purity silicon granules is in the space of suspended state formation separated from one another more than 80%, makes to contain
Silicon gas decomposes the substantial amounts of powder silicon of generation and is carried over reactor with gas, thereby reduces former
The material daily rate of (gas) tooth, adds cost, causes waste, and Si powder enters downstream
Add the intractability to reaction end gas and the cost of the equipment of production, easily cause pollution.
2. in suspension reactor, all of silicon grain need to consume a large amount of gas and cause gas to reclaim
Difficulty, and residual heat of reaction utilization rate is low, adds operation cost.
3, owing to, under reaction temperature (200 DEG C-1400 DEG C), granular silicon surface forms semi-molten
State, the brill company property between granule is very strong, thus can cause intergranular mutual agglomerate,
Thus block reactor air inlet and passage, cause stopping production accident.
4, reactor volume is big, effectively utilizes space little, and production scale is little, increases production and sets
Standby construction cost and difficulty of construction.
5, as seed high purity granular silicon prepare relatively difficult, and in preparation process easily
It is mixed into impurity.
Summary of the invention
It is an object of the invention to provide a kind of reactor producing high purity granular silicon and method,
For realizing ultra-large type, efficient, energy-conservation, continuous, low-cost production high purity granular silicon.
To achieve these goals, the present invention provides a kind of reactor producing high purity granular silicon,
Including:
Reactor cavity；
Solid feed inlet, auxiliary gas entry, unstripped gas it is provided with on described reactor cavity
Body entrance and offgas outlet;Described reactor cavity is internally provided with gas distributor, described gas
Body distributor is used for making auxiliary gas and unstrpped gas be scattered in described reactor cavity;
Described reactor cavity is provided with internal or external preheating mechanism;Described reactor cavity
Outside is provided with tail gas processing mechanism, is connected to described preheating mechanism and enters with described auxiliary gas
Between mouth and unstrpped gas entrance;
Described reactor cavity connects internal or external surface trimming mechanism;Described surface is whole
Reason mechanism carries out surface process for the high purity granular silicon obtaining production;
Described reactor cavity is provided with internal or external heating arrangements and dynamic generation mechanism,
Described dynamic generation mechanism is for making to be positioned at the high purity granular silicon bed of described reactor cavity body
In high purity granular silicon be in relative motion state.
To achieve these goals, the present invention also provides for a kind of according to reaction of the present invention
Device produces the method for high purity granular silicon, including:
Forming high purity granular silicon bed, the high purity granular silicon in described high purity granular silicon bed is close
Collection distribution, filling rate is more than 10%;
Heating described high purity granular silicon bed, the temperature making described high purity granular silicon bed is
100℃-1400℃;The high purity granular silicon in described high purity granular silicon bed is made to be in fortune relatively
Dynamic state;
Being passed through auxiliary gas and unstrpped gas, described auxiliary gas is high-purity H: and/or inertia
Gas, described unstrpped gas is silicon-containing gas, or described unstrpped gas be silicon-containing gas and
Reducing gas H2；
After reaction end gas and supplementary high purity granular silicon heat exchange, press gas through tail gas processing mechanism
After composition separates, it is passed through reactor cavity by auxiliary gas entry or unstrpped gas entrance
Body recycles;After described supplementary high purity granular silicon is heated, enter described reactor cavity
In body;
After the high purity granular silicon obtaining production carries out surface process, cool down collecting packing.
The reactor of the production high purity granular silicon that the present invention provides and method, be used in motion
The high purity granular silicon bed of the dense accumulation of state, it is to avoid the bonding between granular silicon, subtracts
Little reactor volume, and by the high purity granular silicon bed capture reaction tail of dense accumulation
High-purity powder silicon in gas is as seed, and it is supplementary granular for also utilizing the waste heat of reaction end gas
Silicon heats;Achieve ultra-large type, efficient, energy-conservation, continuous, low-cost production high purity granular silicon.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the present invention produces the reactor embodiment of high purity granular silicon;
Fig. 2 is that the present invention produces reactor cavity in the reactor embodiment of high purity granular silicon
Schematic diagram;
It is anti-that Fig. 3 is that the present invention produces a vertical multi-stage in the reactor embodiment of high purity granular silicon
Answer device schematic diagram;
Fig. 4 and Fig. 5 is the cross section optical microphotograph of the high purity granular silicon that the embodiment of the present invention produces
Photo;
Fig. 6 is the X ray diffracting spectrum of the high purity granular silicon that the embodiment of the present invention produces.
Detailed description of the invention
The technical side of the embodiment of the present invention is further illustrated below in conjunction with the accompanying drawings with specific embodiment
Case.
Produce the reactor embodiment of high purity granular silicon
Fig. 1 is the schematic diagram that the present invention produces the reactor embodiment of high purity granular silicon, Fig. 2
The schematic diagram of reactor cavity in the reactor embodiment of high purity granular silicon is produced for the present invention,
Seeing Fig. 1 and Fig. 2, this device includes: reactor cavity 10, preheating mechanism 20, tail gas
Processing mechanism 40, surface trimming mechanism 60, heating arrangements, dynamic generation mechanism.
Reactor cavity 10 is internal can be square, cylindrical or the sky of the various shape such as rectangle
Between, and space can be layered, compartment can split;Reactor cavity 10 could be arranged to directly
Vertical, pin leans on or the placement that lies low, and can carry out following current or counter-current operation when reaction.Work as reaction
When device cavity is upright or leans to place, the height of reactor cavity can be 1-100 rice,
Preferably 1-50 rice, such as: when the height of reactor cavity is 1 meter, reactor can
Thinking 1 grade, it is also possible to for multistage, the height of each of which level is at least 10-20cm;When instead
When to answer the height of device cavity be 50 meters, reactor can be 1 grade or multistage, and height at different levels can
With difference, when reactor is multistage, the height of every one-level is at least 10-20cm;Work as reaction
The height of device is for having determined that value, such as: 50 meters, it is also possible to according to the progression needed for reaction, if
Put the height of every one-level;If reactor is 1 grade, the height of one-level is 50 meters;If reaction
Device is 5 grades, then the height of every one-level is about 10 meters;Same, when reactor cavity
When being highly 70 meters or 100 meters, reactor can also be 1 grade or multistage, can be according to instead
Progression needed for should arranges the height of every one-level, it is also possible to by small size reactor (such as reactor
Housing depth is 1 meter or 50 meters) amplify in proportion, it is also possible to it is multiple small size reactors
Superposition.The size of reactor cavity is determined by the practical situation reacted, reacting gas to be made
By conversion efficiency during reaction bed the highest while the most energy-conservation.Here, the present invention is not limiting as
The height of the height of reactor cavity, such as reactor cavity can also be 1-1000 rice.When
When reactor cavity is for lying low, the length of the most above-mentioned reactor cavity can be 1-100 rice,
Preferably 1-50 rice, specifically description and the above-mentioned reactor cavity to reactor cavity body length
Similar, but can be Two dimensional Distribution then three-dimensional overlay, the reaction that will multiple lie low
Device cavity carries out longitudinal superposition.
The reaction generating high purity granular silicon in the present invention is the endothermic reaction, in order to ensure that heat is not
Scattering and disappearing or few lost, the housing of reactor cavity 10 can be by up of three layers, and internal layer is fire-resistant
Inner bag, intermediate layer is the heat-insulation layer being made up of the insulation material such as refractory fibre and mineral wool,
Outer layer is that box hat plays supporting function.
As in figure 2 it is shown, be provided with solid feed inlet 101 on reactor cavity 10, being used for will
High purity granular silicon as seed joins in reactor cavity 10.
Auxiliary gas entry 102, unstrpped gas entrance it is additionally provided with on reactor cavity 10
105 and offgas outlet.Wherein auxiliary gas is high-purity reducing gas H2And/or noble gas (as
Ar or He), unstrpped gas is high-purity silicon-containing gas, or unstrpped gas is high-purity silicon containing gas
Body and reducing gas H2, silicon-containing gas can be SiH4.SiHCl3,SiCl4,SiH2Cl2...
SiBr4One or more in Deng.The gas used in the present invention (includes unstrpped gas and auxiliary
Helping gas) purity is more than 99.99%.In unstrpped gas silicon-containing gas composition 1% to
100%。
Auxiliary gas entry 102 leads to the gas distributor being positioned within reactor cavity 10
103, unstrpped gas entrance 105 leads to unstrpped gas nozzle 104;Auxiliary gas and unstrpped gas
It is scattered in reactor cavity 10 by gas distributor 103 and unstrpped gas nozzle 104.
The high purity granular silicon as seed added through solid feed inlet 101 tightly packed divides at gas
On cloth device 103, formation high purity granular silicon bed (or, high purity granular silicon bed can not also
It is deposited on gas distributor, and is dependent on reaction cavity diameter and Matter Transfer speed is controlled
The material processed time of staying in every first order reaction cavity);High purity granular silicon as seed
Granule size distribution can have with producing the high purity granular silicon product granularity great Diao distribution obtained
Overlap, i.e. a part can be more than or equal to high-purity as the granularity of the high purity granular silicon of seed
The granularity of grain silicon product, it is preferred that the granularity as the high purity granular polysilicon of seed is big
The little 10-30% for producing the high purity granular silicon product granularity size obtained, wherein produces and obtains
High purity granular silicon product granularity size be according to different applicable cases depending on, typically exist
Between 1-20 millimeter.Concrete, gas distributor 103 is by card (or referred to as sieve plate) and wind
Cap forms, it is also possible to only have one piece of card (porous sieve plate) not have blast cap;Gas distributor
103 can be direct current, effluent, close hole or filled-type distributor.Due to high purity granular silicon bed
The dense accumulation of layer so that the small volume of reactor in the embodiment of the present invention, with existing
Fluidized-bed process is compared, and can increase yield while reducing reactor volume.
Preheating mechanism 20 is arranged on reactor cavity 10 interiorly or exteriorly.As it is shown in figure 1,
In the present embodiment, preheating mechanism 20 is arranged on the outside of reactor cavity 10;Preheating mechanism 20
In have solid inlet, for supplementing as the high purity granular silicon of seed, because the present invention produces
The process of high purity granular silicon is a process consuming seed, so needing constantly to supplement to make
High purity granular silicon for seed;Reaction end gas is given through preheating mechanism 20 and is supplemented as seed
High purity granular silicon heats.
Tail gas processing mechanism 40 is arranged on the outside of reactor cavity 10, and is connected to preheating
Between mechanism 20 and auxiliary gas entry 102 and unstrpped gas entrance 105.Reaction end gas warp
After crossing preheating mechanism 20, entering tail gas processing mechanism 40, tail gas processing mechanism 40 is according to gas
Reaction end gas is separated by body composition, and the gas after then separating is again by auxiliary gas
Entrance or unstrpped gas entrance are passed through in reactor and recycle.
Reaction end gas can carry high-purity powder silicon, because: 1, in reactor running,
High-purity
Grain silicon and/or high purity granular silicon bed draw strong disturbance that granule can be caused to grind
Damage;2, in the present invention, silicon-containing gas pyrolysis itself can generate powder silicon.Due to high in the present invention
Pure granular silicon bed is dense accumulation, so when the preheated device of reaction end gas and vent gas treatment
When mechanism processes Posterior circle to reactor cavity, the high purity granular silicon of dense accumulation in reactor
Powder silicon in bed meeting capture reaction tail gas, thus plays the effect of dust extractor.
Surface trimming mechanism 60 is arranged on reactor cavity 10 interiorly or exteriorly, for right
Produce the high purity granular silicon obtained and carry out surface process.The table of the high purity granular silicon that reaction generates
Face typically ratio is more loose, is easily generated dust, and this can affect downstream production application, thus needs
The surface of this high purity granular silicon is processed so that it becomes dense.Surface dressing machine
Structure 60 is preferably the reaction cavity containing the low concentration reacting gas that concentration is 0-10%, this table
Surface finishing machine structure 60 can be the some sections in reactor.(dense containing low concentration at one
Degree is for 0-10%) in the spouted bed of reacting gas, the surface of high purity granular silicon can form densification
Silicon structure, has thus reached the effect that surface processes, and the surface carried out by which
Processing procedure, will not introduce impurity and other treatment process, reduce production cost.Certainly,
Surface treatment process can also use traditional pickling, cleaning and drying course.
Heating arrangements is arranged on reactor cavity 10 interiorly or exteriorly.In order to make reaction reach anti-
Answer temperature, need reactant is heated.Heating arrangements is preferably and high purity granular silicon bed
The power supply of layer electrical connection, i.e. to high purity granular silicon bed plus voltage, due to the quasiconductor of silicon
Performance, the heating of high purity granular silicon bed causes the temperature of high purity granular silicon bed to raise.Use
The method is for directly heating, and the thermal efficiency is high, and heat utilization efficiency is high, uses and high-purity draws shape silicon conduct
Heater also can be avoided polluting, it is ensured that product purity.
Heating arrangements can also use other multiple existing mode of heating: 1) resistance wire (silicon rod,
The materials such as high-purity alpha-SiC, high-purity Si N or graphite) directly heat;2) microwave, plasma, laser
Or the heating indirectly such as sensing;3) combustion heating that indirectly provided by muffle heat radiation tube or return
Converter kiln heats;4) using heat exchanger in external jacket and bed, external jacket heat exchanger can use electricity
Sense heating and thermophore parallel operation, in bed, heat exchange can use thermophore heating, electrical induction
With modes such as electrode bar heating;5) external heat mode, such as by reactant required in reaction
(such as levitation gas and silicon grain itself) is re-introduced into reactor after external heat;6) coupling type is anti-
Should heat, use chemical reaction such as chlorine (C12) or hydrogen chloride (HCl) join system.
In order to when producing high purity granular silicon, make high purity granular silicon be not easy the present invention that bonds
Reactor also include for making the high purity granular silicon in high purity granular silicon bed be in relatively fortune
The dynamic generation mechanism of dynamic state, dynamic generation mechanism be arranged on reactor cavity 10 internal or
Outside.Preferably, dynamic generation mechanism is gas assist nozzle and/or unstrpped gas nozzle;
This gas assist nozzle and unstrpped gas nozzle are arranged in reactor cavity 10, respectively with auxiliary
Gas access is helped to be connected with unstrpped gas entrance, for gas and unstrpped gas injection will be assisted
Enter agitation in reactor cavity 10 high father is angry to draw shape silicon bed, make in high purity granular silicon bed
High purity granular silicon is in relative motion state, it is to avoid the bonding between high purity granular silicon;And
Owing to unstrpped gas is through being injected into high purity granular silicon bed, cause at high purity granular silicon bed
Middle contact and the high purity granular near gas distributor are practised disconnected neutron and reaction are less likely to occur, by
This, can be avoided gas distributor 103 blocked.
This dynamic generation mechanism can also be accomplished by making high purity granular silicon bed
Be in dynamically: 1) introduce external force carry out as spouted, rotate, stir, mix, vibrate or make height
Pure granular silicon bed flows under gravity by the staggered comb castor structure etc. installed on inwall;2)
Reactor is made to be under other gravitational fields (such as centrifugal force field etc.);3) forced fluidized bed is used;4) make
With vibrated fluidized bed (including mechanical vibration, sound wave or ultrasonic activation, plug-in type vibrating etc.).
Further, for the high-purity powder silicon in more preferable capture reaction tail gas and made
For supplementary high purity granular silicon seed, the reactor of the present invention also includes gas solid separation mechanism
30.Gas solid separation mechanism 30 is arranged on reactor cavity 10 either internally or externally, and with
Preheating mechanism 20 connects.The reaction end gas discharged from reactor cavity 10 is through gas solid separation
Mechanism 30 captures high-purity powder silicon, and this high-purity powder silicon is returned to reactor cavity 10
Middle again participation as seed is reacted or is kneaded on high purity granular silicon grain.
Wherein (filling rate is more than 50, is preferably in gas solid separation mechanism 30 preferably intensive stacking
High purity granular silicon granular layer 50-80%), such as, this high purity granular silicon granular layer is the most permissible
For: intensive for high purity granular silicon grain is deposited in the many silicone tubes (or earthenware) with boring
In, and at its outer cladding glass cloth, these silicone tubes are divided into array to hang on reactor expanding reach
Top or reactor outside.Reaction end gas i.e. passes through fine and close by gas solid separation mechanism
During high purity granular silicon granular layer, the high-purity powder silicon carried in reaction end gas can be captured,
Use this gas solid separation mechanism, be possible not only to prevent high-purity powder silicon from entering reaction downstream, and
And can generation high purity granular silicon seed simple, free of contamination.Wherein, filling rate is high-purity
The ratio that the packing space of granular silicon is taken up space with it, filling rate and grain shape and granule chi
Very little distribution is relevant;Filling rate be not for whole reaction cavity for, such as, work as filling
When rate is 70%, reaction cavity can only have 20% to be filled.
Certainly, gas solid separation mechanism 30 can also take other form to reach gas solid separation
Effect, such as: 1), by changing reactor inside diameter size, make reactor head amplify and change
Short grained escape velocity, it is achieved sedimentation capture;2) cyclone separator is used;3) filter is used
Or cleaner unit.
In order to make the even particle size of the high purity granular silicon produced, the reactor of the present invention
Screening mechanism 50 can also be included.Screening mechanism 50 is arranged at the inside of reactor cavity 10
Or outside, it is connected between reactor cavity 10 and surface trimming mechanism 60.Reaction is raw
The high purity granular silicon become is incorporated in screening mechanism 50 and screens, by oversized particles through grinding
Send back to preheating mechanism 20 after broken together with too small granule, heated after return to reactor cavity
Internal continued growth, be up to granular size require high purity granular silicon select feeding next at
Science and engineering section, thus can control the size of product particle in required optimum size scope
In, (when granule is less, meeting is bigger due to it to be possible not only to reduce possible surface contamination
Surface area and easily receive pollution), be more favorable to downstream produce in application.Sieving and following
To avoid high purity granular silicon and other non-silicon element material particularly metal during ring as far as possible
Directly contact, to prevent from reducing product quality because impurity pollutes.
Mode in order to provide other supplements the high purity granular silicon as seed, and the present invention's is anti-
Pulveriser 70, pulveriser 70 are connected to screening mechanism 50 and preheating machine to answer device to include
Between structure 20, pulverize for the high purity granular silicon that a part is screened out.
The present invention produces during high purity granular silicon, high-purity draws shape silicon seed to be in not
In disconnected consumption, when being not enough to by gas solid separation mechanism 30 isolated high-purity powder silicon amount
In post-reactor during the consumption of high purity granular silicon seed, will be screened out by pulveriser 70
Big of high purity granular silicon draws in row pulverizing, pulverizes the little granule generated again through preheating mechanism 20
After heating in Returning reactor cavity 10.Owing to the present invention containing in the high purity granular silicon of generation
Having hydrogen, therefore pulveriser can also make high-purity by heating rapidly hydrogeneous high purity granular silicon
Grain silicon explosion forms little granule as seed.This pulveriser 70 can also is that high-speed gas crushes
Device, sonicator or pulverize with the dust-precipitator existing pulveriser such as (whirlwind, cloth bag).
In order to reduce the siliceous deposits on reactor cavity inwall, reactor cavity of the present invention
Inside be also provided with the gas curtain tangent with reactor cavity inwall (by or do not pass through inwall) machine
Structure, this air curtain mechanism is covered in the gas curtain of reaction cavity inwall for producing;This air curtain mechanism has
Body can be: on reactor cavity body wall, cuts multiple the least with the angle of inner wall surface
Bar shaped blow vent, this bar shaped blow vent can be laterally or longitudinally, by reactor cavity
Outside is passed through not after silicon-containing gas (noble gas), this not silicon-containing gas led to by multiple bar shapeds
After QI KOU enters reactor cavity inside, it is possible to form one and be covered in reaction cavity inwall
And the gas curtain tangent with inner wall surface, this gas curtain can stop silicon-containing gas in reactor cavity
Reactor cavity inwall deposits silicon;This air curtain mechanism can also be specifically at reactor cavity
Internal bottom or top arrange the annular being connected with outside not silicon-containing gas (noble gas)
Pipe, outputs the several bar shaped pores parallel with reactor cavity inwall, at ring on ring pipe
Shape pipe is passed through not after silicon-containing gas, formed one be covered in reaction cavity inwall and with inwall table
The gas curtain that face is tangent, this gas curtain can hinder grade reactor cavity in silicon-containing gas at reactor cavity
Silicon is deposited on internal wall.
The reactor that the embodiment of the present invention provides can also include monitoring and central control system,
The concrete technology parameter of link each to reaction unit carries out record, when concrete technology parameter surpasses
Can give a warning and provide after spending normal range and be automatically adjusted, wherein reactor needs mensuration
Parameter has: temperature at the bottom of bed (including gas and solid temperature), exit gas (reaction end gas) composition,
Pressure, solid granularity, bed density, heat transfer and mass transfer, the direction of motion etc. of solid particle.
Reactor cavity and preheating mechanism in the embodiment of the present invention can use horizontal or vertical
To multistage multidimensional structure (gas nozzle in Fig. 2 can be multiple and divide in two-dimensional array
The gas nozzle of cloth), the order of reaction can be 1-50 level, and preferably 1-20 level is more excellent
For 3-10 level, to increase effective reaction time and heat exchange efficiency, reduce powder silicon and be carried over,
Reduce reactor dimensions and construction cost.When reaction is multistage, the reaction tail in every one-level
Gas may be by its waste heat and draws shape silicon to heat to high-purity in next stage so that heat exchange
Efficiency increases, and adds effective reaction time;Such as, when reaction is 3 grades, heat exchange is imitated
Rate improves 60%, and effective reaction time adds 3 times;When reaction is 6 grades, heat exchange is imitated
Rate improves 80%, and effective reaction time adds nearly 6 times.
It is anti-that Fig. 3 is that the present invention produces a vertical multi-stage in the reactor embodiment of high purity granular silicon
Answer device schematic diagram.See Fig. 3, process prescription when reacting to using multistage reactor
As follows: high purity granular silicon seed autoreactor top preliminary heater 201 step by step by multistage instead
Answer the tail gas heating in device, when high purity granular silicon seed is preheated device and primary heater
2031 be heated to temperature required after, enter in first order reactor 2021, and with contain
Silicon gas reacts so that high purity granular silicon seed its own face grows upper high-purity silicon layer,
(nitrogen can be used in order to reduce dangerous auxiliary gas), the temperature of this high purity granular silicon seed
Because take part in endothermic decomposition reaction and step-down, this high purity granular silicon seed drops to the second level
Heater 2032 enters second level reactor 2022 after heating and reacts, same,
This high purity granular silicon seed drops to entrance the 3rd after third level heater 2033 heats
Stage reactor 2023 reacts, and through this reaction of high order, the granularity of high purity granular silicon is gradually
Grow up.
Need explanation have following some:
First, reacting gas flows to flow to vertical with particle, it is also possible to flow to particle
In any angle;Second, rely on the diameter of reaction cavity and Matter Transfer speed to control material
The time of staying in every first order reaction cavity;3rd, silicon-containing gas all can in each order reaction
Producing powder silicon, these powder silicon parts enter final stage preheater with reaction end gas, then
(the high-purity of dense accumulation draws shape silicon to step up the gas solid separation mechanism that is eventually preheated in device
Granular layer) powder silicon all stopped the descending novel species as reaction together with high purity granular silicon
Sub-granule;4th, some powder silicon can go downwards to along with high purity granular silicon pinch the most always
Close in reactor 204, so that powder silicon (i.e. powder in the presence of not having silicon-containing gas
End silicon is in the presence of an inert gas) it is kneaded on big high purity granular silicon face, make
The granule of high purity granular silicon grow up further, ball-type, thus avoid at high purity granular silicon
A large amount of dust is had, so that operating difficulties affects subsequent handling after entering sifter 205;High-purity
After grain silicon screened device 205 screening, big granule enters into surface dressing device 206,
Wherein by the silicon-containing gas that concentration is relatively low, high purity granular silicon face is carried out dense coating, thus
The surface-brightening making each high purity granular silicon is clean and tidy;The high purity granular after surface dressing will be carried out
After the cooling of silicon cooled device 207, enter packer 210 and pack;Sieved by sifter 205
Little granule after choosing is returned to preliminary heater 201 by conveying mechanism 208, thus completes whole
Individual circulation.Lower temperature is had been cooled to such as by preliminary heater 201 tail gas out
100-200C, due to each preheater powder filter effect, in tail gas, the degree containing powder silicon is relatively
Low, after entering Reconstruction of End Gas Separator 209, may be logically divided into high-purity gas and mix with unstrpped gas
Further inject into and return among reactor, thus complete another circulation;Wherein first passage
200 is unstrpped gas entrance, and second channel 220 is auxiliary gas entry.
Silicon is polluted for reactor material is reduced or avoided and has enough under the high temperature conditions
Mechanical strength, the embodiment of the present invention provide reactor in, the material of each several part can be selected for
Lower material: HIGH-PURITY SILICON, high-purity silicon carbide, high purity silicon nitride, quartz or graphite etc. are at high temperature
Diffusion impurity will not enter the material in reactor.
In embodiments of the present invention, the combination such as reactor and preheating mechanism can be done directly
Connecing in succession, i.e. preheater, filter, reactor, kneading and surface dressing etc. can be one
The different sections of individual overall cavity, it is also possible to reactor and preheating mechanism etc. separately, especially
It is the corresponding some reactors of a set of preheating mechanism, thus can be implemented in one of them reactor
When keeping in repair, other reactor can remain in operation, and decreases the off-time.
Below in conjunction with Fig. 1 and Fig. 2, describe the present invention and produce the reactor of high purity granular silicon in fact
Execute the operating process of example.
Before starting reaction first, add high purity granular silicon kind by solid feed inlet 101
Son, high purity granular silicon seed natural packing forms intensive high purity granular silicon bed, high-purity grain
Shape silicon bed is heated mechanism heats to reaction temperature.
High-purity reacting gas (silicon-containing gas and reducing gas H2) add by pump (pump) via mixing
Pressure spurts into high purity granular silicon bed from unstrpped gas nozzle 104, assists levitation gas simultaneously
Hydrogen and/or noble gas are also printed ump by blast apparatus) pass through from auxiliary gas entry 102
Gas distributor 103 is passed through in reactor cavity 10;Reacting gas is in reactor cavity 10
Reaction, silicon-containing gas generation pyrolysis generates silicon and is wrapped in the table of high purity granular silicon seed
Face so that high purity granular silicon seed is constantly grown up;The reaction tail discharged from reactor cavity 10
Gas enters preheating mechanism 20 and gas-solid separating mechanism 30, and gas solid separation mechanism 30 separates and collects
Go out the powder silicon carried in reaction end gas, and reaction end gas utilizes by preheating mechanism 20 remaining
Heat gives granule and the heating of powder silicon, and the HIGH-PURITY SILICON after heating is returned to reactor cavity 10
In again participate in reaction;The reaction end gas discharged from preheating mechanism 20 enters vent gas treatment machine
Structure 40, reaction end gas is separated, then by tail gas processing mechanism 40 according to gas ingredients
Gas after separating is passed through reactor by reaction gas inlet or auxiliary gas entry again
Cavity recycles;High-purity silicon granules (the relative size granularity generated in reactor cavity 10
Bigger) elevated mechanism 35 takes screening mechanism 50 to, size after screening mechanism 50 screens
Suitably enter surface trimming mechanism 60 after high purity granular silicon and carry out surface process, then through cold
But enter package mechanism 90 after mechanism 80 cooling to carry out packing and completing whole production process,
After the lower high purity granular silicon little granule the most preheated mechanism 20 of screened mechanism 50 screening heats
Returning reactor cavity 10 re-starts reaction.Wherein, not enough at high purity granular silicon seed
Time, a part of HIGH-PURITY SILICON bulky grain that can be filtered out by screening mechanism 50 adds pulveriser
In 70, after the high purity granular silicon of pulveriser 70 pulverizing generation heats via preheating mechanism,
Return in reactor cavity as high purity granular silicon seed.
In order to make it easy to understand, in the embodiment of the present invention to reactor cavity, gas solid separation mechanism,
Preheating mechanism, screening mechanism, surface trimming mechanism etc. are respectively described, and in reality
Generation during, above-mentioned all parts can be to be integrally disposed upon in a reactor cavity body.
The reactor producing high purity granular silicon that the embodiment of the present invention provides, is used in motion
The high purity granular silicon bed of the dense accumulation of state, it is to avoid the bonding between granule, reduces
Reactor volume, and by the high purity granular silicon bed capture reaction tail gas of dense accumulation
In high-purity powder silicon as seed, the waste heat also utilizing reaction end gas is supplementary high-purity grain
Shape silicon seed heats;Achieve ultra-large type, efficient, energy-conservation, continuous, low-cost production is high-purity
Grain silicon.
The reactor utilizing the present invention to provide produces the embodiment of the method for high purity granular silicon
Seeing Fig. 1 and Fig. 2, the reactor utilizing the present invention to provide produces high purity granular silicon
Embodiment of the method, including:
High purity granular silicon seed is added in reactor cavity 10 from solid feed inlet 101 and is formed
High purity granular silicon bed, the high purity granular silicon seed in high purity granular silicon bed is that intensive state is divided
Cloth, filling rate is more than 10%, preferably more than 50%.In order to make high purity granular silicon bed
Free space between middle granule is less, can take pressurization, spouted bed and descending moving bed
Deng operation, concrete measure can also include: 1) by controlling valve raising gas speed, uses thinner
The granule of granularity, makes bubbling bed be converted into turbulent bed;2) granule degree of drawing structure is improved, to high-purity
Granularity and the particle size distribution of granular silicon are in optimized selection, and make gas-solid aggregative fluidized bed dissipate formula,
Reduce mean diameter, add wide particle diameter distribution or increase thin content and can improve fluidization quality, as
Increase bed expansion degree, improve biphase exchange capacity, alleviate short circuit phenomenon, and likely
Save internals;3) use pressurization, under pressure is higher than an atmospheric pressure, not only can increase
Add treating capacity, and owing to decreasing the difference of density of solid and gas density;4) use the most carefully
Granule, can reduce back-mixing, improves biphase contacting efficiency, augmentation of heat transfer, uses production capacity
Improve;5) in, circulation Kongxiang is spouted, at the built-in self-circulation system of reactor, makes granule, bed
Intensive and do not tie pipe;6) moving bed (vertically and horizontally, incline and tremble) increases packing density of particle, subtracts
Lack free space thus decrease gas phase powder and generate with powder quick to the polymerization of granule.
Heating high purity granular silicon bed, making high purity granular silicon bed temperature is 100 DEG C-1400 DEG C,
It is preferably 300 DEG C-1200 DEG C.These heating means can be by high purity granular silicon bed and power supply
Electrical connection, i.e. gives high purity granular silicon bed making alive, utilizes silicon self-resistance heat release to carry out
Heating.Equally, it is also possible to be similar in Siemens Method use high purity silicon rods electrified regulation.
When producing high purity granular silicon, in order to make silicon grain be not easy bonding, need to make high-purity
High purity granular silicon in granular silicon bed is in relative motion state.Can be by the following method
Realization makes high purity granular silicon be in relative motion state: 1) will auxiliary gas and/or unstrpped gas
Spurt in reactor cavity 10, make high purity granular silicon bed be kept in motion;2) introduce
External force carry out as spouted, rotate, stir, mix, vibrate or flowing etc. under gravity;3) make instead
Device is answered to be under other gravitational fields (such as centrifugal force field etc.);4) agitated bed is used;5) vibrated bed is used
(including mechanical vibration, sound wave or ultrasonic activation, plug-in type vibrating etc.).
Led to through gas distributor 103 by auxiliary gas entry 102 and unstrpped gas entrance 105
Entering to assist gas and unstrpped gas, auxiliary gas is H2And/or noble gas, unstrpped gas
Can be silicon-containing gas, or unstrpped gas can also be silicon-containing gas and reducing gas H2。
Reaction pressure in reactor cavity 10 is 0.1-100 atmospheric pressure, preferably 0.1-50
Individual atmospheric pressure.
The flow of auxiliary gas and unstrpped gas is not floated flow velocity and is limited by conventional fluidization bed is minimum
System, air-flow can be less than critical fludization velocity (Umf), and air velocity can control 0.01
Between Umf-10Umf.Thus can bring following benefit: save air-flow, reduce heating and energy
Amount loss, reduces vent gas treatment amount, reduces and pollutes;Make the opereating specification when producing of the present invention
Greatly, gas is the amount doesn't matter, will not stop production because of interim minimizing of raw material.
Reaction end gas is given through preheating mechanism 20 and is supplemented the high purity granular silicon heating as seed;
The high purity granular silicon supplemented through heating returns in reactor cavity 10.
Reaction end gas enters tail gas processing mechanism 40 through preheating mechanism and separates, and isolates
Gas according to gas ingredients again by auxiliary gas entry 102 or unstrpped gas entrance 105
It is passed through in reactor cavity 10 and recycles.When tail gas is returned to reactor cavity through circulation
Time in 10, through high purity granular silicon bed, gas now to generally carry high-purity powder
Silicon, high purity granular silicon bed then i.e. can pass through high purity granular when gas as dust extractor
During silicon bed, the high-purity powder silicon wherein carried can be captured and stay high purity granular silicon bed
Middle as high purity granular silicon seed.
The high purity granular silicon product that reaction obtains carries out surface process through surface trimming mechanism 60
After, collect after cooling;Wherein, the process that this surface processes can be high purity granular silicon product warp
Cross the reaction cavity containing the low concentration unstrpped gas that concentration is 0-10% so that at high-purity
The silicon structure of the Surface Creation densification of grain silicon product.
Further, for the high-purity powder silicon in more preferable capture reaction tail gas, and by it
As supplementary high purity granular silicon seed, the method that the present invention produces high purity granular silicon is all right
Isolate, through gas solid separation mechanism 30, carry in reaction end gas high-purity including: reaction end gas
Powder silicon, this process can be that reaction end gas is through intensive stacking (filling rate is more than 50%)
High purity granular silicon granular layer isolates high-purity powder silicon;This process is possible not only to prevent high-purity powder
End silicon enters reaction downstream, and can generation simple, free of contamination is high-purity draws shape silicon seed.
In order to make the size of high purity granular silicon grain produced uniform, the present invention produces high-purity
The method of grain silicon can also include: reacted bigger high purity granular silicon grain is boosted
Machine or send passage to be delivered in screening mechanism 50 steathily, obtains granular size by screening and conforms to
The high purity granular silicon bulky grain asked, and by undesirable for granular size high purity granular silicon warp
Reaction is continued in returning to reactor cavity body after preheating mechanism heating.Thus can be by product
The size of grain controls in the range of required optimum size, is possible not only to reduce possible table
Surface pollution (when granule is less, can easily receive pollution due to its bigger surface area), also
More there is tooth!" in downstream produce in application.To avoid silicon in screening and cyclic process as far as possible
Grain directly contacts with other element material particularly metal, to prevent from dropping because impurity pollutes
Low production quality.The embodiment of the present invention produces the granularity of the high purity granular silicon grain obtained 1
Between mm-20cm, preferred granularity is between 3mm-5mm, and crystal degree is not more than granularity
30%, preferred crystal degree is 1-500 nanometer.Crystal degree is the medium and small single crystal ingot of granule
Yardstick, example: granularity is that the polycrystalline of 2mm draws and can be differed by a lot of crystal degree
The little single crystal grain composition of (between 1-500 nanometer).It is high-purity that embodiment of the present invention production obtains
The density of grain silicon granule is preferably 1-2.4g/cm3。
Further, after supplementing high purity granular silicon seed by gas solid separation mechanism 30, reaction
During the still deficiency of the high purity granular silicon seed in device cavity 10, can supplement in the following manner
High purity granular silicon seed: the high purity granular silicon bulky grain that part screening obtains is passed through grinding
Pulverizing in device 70 is high purity granular silicon grain, then by this high purity granular silicon grain by preheating
Mechanism 20 heat after in Returning reactor cavity 10 as high purity granular silicon seed.
It is 1-50 level that the embodiment of the present invention produces the order of reaction of high purity granular silicon, preferably 1
-20 grades, more excellent for 3-10 level.
During the embodiment of the present invention generates high purity granular silicon, by the following method to thing
Material is transmitted or fills but: 1) gravity flow method, i.e. the gravity by solids self flows into bed
Layer and the method flowed out from bed, wherein in order to make solids successfully flow, Ke Yi
The appropriate point of pipeline is passed through a small amount of gas, makes solids loosen so that flowing;2) machinery
Conveying method, the machinery generally used has: screw rod conveyor, belt feeder, disk feeder,
Star feeder and bucket elevator etc.;3) aerodynamic force conveying method.
What the present invention provided utilizes the reactor of the present invention to produce the method enforcement of high purity granular silicon
Example, be used in the high purity granular silicon bed of the dense accumulation of kinestate, it is to avoid granule
Between bonding, reduce reactor volume, and by the high purity granular silicon of dense accumulation
High-purity powder silicon in bed capture reaction tail gas, as seed, also utilizes the remaining of reaction end gas
Heat is the high purity granular silicon heating supplemented;Achieve ultra-large type, efficient, energy-conservation, continuous, low
Cost produces high purity granular silicon.
The present invention is given below and produces an experimental example of high purity granular silicon
10 kilograms of diameters are placed in a diameter of 15cm at the high purity granular silicon seed of 0.1-2mm
Barrel-shaped reactor in, with middle frequency furnace, reactor is heated simultaneously.Leafy by one
High purity granular silicon seed in reactor is stirred by sheet agitator, makes whole high purity granular silicon
Bed is in dense accumulation but has the state of mutually motion between granule, in temperature is
During 6000C-6800C, it is passed through the silicon-containing gas silane that concentration is 50%-75%, during experiment
Between be 6.5 hours, experiment end is weighed granule in reactor, and total weight adds 4.35
Kilogram, one kilogram of silicon power consumption of average production is 3.45 kilowatts, and silane conversion efficiency is 98%.
Table 1 gives the specific experiment that two kinds of different reactors of application produce high purity granular silicon
The comparison of data.Wherein, experiment 2 is the experiment that the application embodiment of the present invention is carried out.
The experimental data of two kinds of different reactors applied by table 1
| Experiment 1 | Experiment 2 | |
| Reactor | Loose spouted bed | Intensive vibrated bed |
| Temperature (DEG C) | 600-680 | 600-680 |
| Silane is composition in argon | 10% | 50-75% |
| Silicon grain gross weight increases (gram) | 990 | 4350 |
| Response time (hour) | 10 | 6.5 |
| Silane conversion efficiency (%) | 79.5 | 98 |
| Per kilogram product power consumption (kwh/kg) | 12 | 3.45 |
Fig. 4 and Fig. 5 is the cross section optical microphotograph of the high purity granular silicon that the embodiment of the present invention produces
Photo.See Fig. 4 and Fig. 5 and can be seen that the first seed 401 being positioned at high purity granular silicon center
With second seed 501, and the first grown layer 403 and second being wrapped in seed peripheral is raw
Long layer 503.In the diagram, big between the first grown layer 403 and the first seed 401
Measuring granular wrappage 402 high-visible, these granular wrappages 402 are the powder that gas phase generates
End silicon, in the reaction, these powder silicon are deposited among big granular silicon, here it is this
Described in inventive embodiments, powder silicon is mediated the kneading effect among granular silicon;By portion
Divide powder silicon to fall in granular silicon, thus accelerate response speed, improve efficiency, reduce entirety
Energy consumption.
Fig. 6 is the X-ray diffracting spectrum of the high purity granular silicon that the embodiment of the present invention produces, and sees
Fig. 6, it can be seen that the characteristic spectral line (half-peak breadth is at 0.12 degree) of more sharp-pointed silicon, this shows
The crystal grain of the silicon that the present invention produces is more than 1.0 μm.
During the high purity granular silicon producing the embodiment of the present invention and commercial electronic grade particles silicon are carried out
Sub-activation analysis, table 2 gives the application high purity granular silicon product that the embodiment of the present invention produces
With the analysis of components of heavy metal in commercial electronic grade particles silicon, unit is 1/1000000th.By
Table 2 understands, the high purity granular silicon product that the embodiment of the present invention produces and commercial electronic grade particles
In silicon, the content of impurity is suitable, and the high purity granular silicon product that i.e. embodiment of the present invention produces reaches
The standard of commercial electronic grade particles silicon.
Table 2 commercial electronic grade particles silicon compares with experimental products impurity composition of the present invention
| Element | Commercial electronic grade particles silicon | Experimental products of the present invention |
| A | 4.13E-04 | |
| Au | 2.75E-06 | 1.16E-06 |
| Ce | 3.08E-03 | 2.60E-03 |
| Ga | 3.33E-04 | 3.87E-04 |
| La | 1.90E-05 | 3.68E-04 |
| Mo | 3.71E-03 | 2.33E-03 |
| Sc | 3.76E-05 | |
| Sm | 1.74E-05 | |
| Th | 2.20E-04 | |
| U | 8.47E-05 | |
| W | 5.00E-04 |
Last it is noted that above example is only in order to illustrate technical scheme, and
Non-to its restriction;Although the present invention being described in detail with reference to previous embodiment, ability
The those of ordinary skill in territory is it is understood that it still can be to described in foregoing embodiments
Technical scheme is modified, or wherein portion of techniques feature is carried out equivalent;And these
Amendment or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention skill
The spirit and scope of art scheme.
Claims (14)
1. the method producing high purity granular silicon, including:
A. in reaction chamber, high purity granular silicon bed is formed, in described high purity granular silicon bed
High purity granular silicon dense distribution, filling rate is more than 10%；
B. heating described high purity granular silicon bed, the temperature making described high purity granular silicon bed is
100 DEG C-1400 DEG C；
C. it is passed through auxiliary gas and unstrpped gas, makes auxiliary gas and unstrpped gas spurt into instead
Answer agitation high purity granular silicon bed in device cavity, make the high purity granular in high purity granular silicon bed
Silicon is in relative motion state；Make the method that described high purity granular silicon bed is kept in motion
For: in auxiliary gas and/or unstrpped gas are spurted into described reactor cavity body spouted, rotate,
Stir, mix, vibrate, make high purity granular silicon bed flow under gravity by pacifying on inwall
The staggered comb structure of dress；Described auxiliary gas is high-purity H2And/or noble gas, described
Unstrpped gas is silicon-containing gas and reducing gas H2, silicon-containing gas generation pyrolysis generates
Silicon is wrapped in the surface of HIGH-PURITY SILICON granular silicon seed, and produced reaction end gas is discharged；
The reaction end gas discharged from reactor cavity captures high-purity powder through gas solid separation mechanism
Silicon, and this high-purity powder silicon returns to again participate in as seed in reactor cavity reaction；
When the amount of described high-purity powder silicon is sufficient to compensate for the consumption of high purity granular silicon seed in reactor
Time, by pulveriser, the high purity granular silicon bulky grain screened out is pulverized, pulverize and generate
Little granule again after preheating mechanism heats in Returning reactor cavity or pulveriser passes through
Heat rapidly hydrogeneous high purity granular silicon, make high purity granular silicon explosion form little granule as seed.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
Heating high purity granular silicon bed choosing is freely directly to silicon grain bed electrified regulation, by resistance wire
Directly heat, by microwave, laser or sensing heating indirectly, muffle heat radiation tube provided
Combustion heating or kiln heating, in external jacket and bed in heat exchanger mode at least one
Make the described heated temperature of granular polycrystalline silicon bed between 100-1400 DEG C；Described outer clip
Set heat exchanger uses inductive heating and thermophore parallel operation, and in described bed, heat exchange uses thermophore to add
Heat, electrical induction and electrode bar heating.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
Noble gas is He gas or argon, and raw material silicon-containing gas is SiH4、SiHCl3、SiCl4、
SiH2Cl2、SiBr4In one or more.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
In unstrpped gas, silicon-containing gas composition is 1-100%, and the reaction pressure in reaction cavity is
0.1 to 100 atmospheric pressure.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
Reactor cavity is set to uprightly, leans to or lies low placement, carries out following current or inverse when reaction
Flow operation.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
The air velocity of described auxiliary gas and unstrpped gas is 0.01 to 10 times of critical fludization velocities.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
Described gas solid separation mechanism has the high-purity silicon granules bed that filling rate is more than 50%.
The method of production high purity granular silicon the most according to claim 1, it is characterised in that
High purity granular silicon production obtained is by containing the low concentration reacting gas that concentration is 0-10%
Surface trimming mechanism carry out surface dressing.
The method of production high purity granular silicon the most according to claim 8, it is characterised in that
The granularity of the high purity granular silicon grain that described method finally obtains is between 1mm-20cm.
The method of production high purity granular silicon the most according to claim 8, its feature exists
In, the density of the high purity granular silicon grain that described method finally obtains is 1g/cm3-2.4g/cm3。
The method of 11. production high purity granular silicons according to claim 1, its feature exists
In, solid particle is transmitted by gravity flow method, machinery conveying method or aerodynamic force conveying method.
12. according to the arbitrary described method producing high purity granular silicon of claim 1-11, its
Being characterised by, reactor cavity height is 1-100 rice.
The method of 13. production high purity granular silicons according to claim 12, its feature exists
In, the order of reaction is 1-50 level.
The method of 14. production high purity granular silicons according to claim 12, its feature exists
In, the material of reactor each several part is selected from HIGH-PURITY SILICON, high-purity silicon carbide, high purity silicon nitride,
Quartz or graphite.
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| US8790048B2 (en) * | 2008-11-14 | 2014-07-29 | J-Power Entech, Inc. | Lock hopper |
| CN101869981B (en) * | 2010-06-19 | 2012-01-25 | 太原理工大学 | Microwave-heated spouted fluidized decarbonization device |
| CN102530951B (en) * | 2010-12-24 | 2016-01-20 | 江苏中能硅业科技发展有限公司 | Produce method and the device of granular polycrystalline silicon |
| DE102011003875A1 (en) * | 2011-02-09 | 2012-08-09 | Wacker Chemie Ag | Method and device for dosing and packaging polysilicon fragments as well as dosing and packaging unit |
| KR101538205B1 (en) * | 2011-09-16 | 2015-07-24 | 주식회사 엘지화학 | Gas providing nozzle having a property of heating and apparatus for manufacturing polysilicon comprising the same |
| CN102730694A (en) * | 2012-06-11 | 2012-10-17 | 江苏双良新能源装备有限公司 | Reduction furnace bell gas curtain heat-insulating and energy-saving structure |
| CN107857269B (en) | 2012-12-31 | 2020-06-26 | 各星有限公司 | Improved operation of fluidized bed reactors by optimizing temperature gradients via particle size distribution control |
| CN103183324B (en) * | 2013-01-23 | 2014-12-31 | 青海拓海新材料有限公司 | Unit for preparing silicon nitride product by silica powder recovered from crystalline silicon processed waste mortar |
| DE102013206236A1 (en) | 2013-04-09 | 2014-10-09 | Wacker Chemie Ag | Gas distributor for Siemens reactor |
| DE102013209076A1 (en) * | 2013-05-16 | 2014-11-20 | Wacker Chemie Ag | A reactor for producing polycrystalline silicon and a method for removing a silicon-containing deposit on a component of such a reactor |
| DE102013210039A1 (en) * | 2013-05-29 | 2014-12-04 | Wacker Chemie Ag | Process for producing granular polysilicon |
| US10525430B2 (en) | 2013-12-26 | 2020-01-07 | Bruce Hazeltine | Draft tube fluidized bed reactor for deposition of granular silicon |
| US9050604B1 (en) | 2014-06-06 | 2015-06-09 | LLT International (Ireland) Ltd. | Reactor configured to facilitate chemical reactions and/or comminution of solid feed materials |
| US9724703B2 (en) | 2014-06-06 | 2017-08-08 | LLT International (Ireland) Ltd. | Systems and methods for processing solid materials using shockwaves produced in a supersonic gaseous vortex |
| DE102014221928A1 (en) | 2014-10-28 | 2016-04-28 | Wacker Chemie Ag | Fluidized bed reactor and process for producing polycrystalline silicon granules |
| DE102015206849A1 (en) | 2015-04-16 | 2016-10-20 | Wacker Chemie Ag | Apparatus and method for classifying and dedusting polysilicon granules |
| US9452434B1 (en) | 2015-04-17 | 2016-09-27 | LLT International (Ireland) Ltd. | Providing wear resistance in a reactor configured to facilitate chemical reactions and/or comminution of solid feed materials using shockwaves created in a supersonic gaseous vortex |
| US10427129B2 (en) | 2015-04-17 | 2019-10-01 | LLT International (Ireland) Ltd. | Systems and methods for facilitating reactions in gases using shockwaves produced in a supersonic gaseous vortex |
| KR101579134B1 (en) | 2015-07-02 | 2015-12-21 | 주식회사쎄인텍 | Apparatus for Manufacturing High Purity Nano-Powder |
| US10434488B2 (en) | 2015-08-11 | 2019-10-08 | LLT International (Ireland) Ltd. | Systems and methods for facilitating dissociation of methane utilizing a reactor designed to generate shockwaves in a supersonic gaseous vortex |
| DE102015215858B4 (en) * | 2015-08-20 | 2019-01-24 | Siltronic Ag | Process for heat treatment of granules of silicon, granules of silicon and process for producing a single crystal of silicon |
| CN105819449B (en) * | 2016-03-21 | 2018-07-20 | 中国成达工程有限公司 | Silane moving-burden bed reactor and the method that granular polycrystalline silicon is produced using the reactor |
| WO2017172745A1 (en) * | 2016-03-30 | 2017-10-05 | Sitec Gmbh | Mechanically vibrated packed bed reactor and related methods |
| CN106154963A (en) * | 2016-08-11 | 2016-11-23 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of frequency-changing control system of feed mechanism |
| US9962672B1 (en) | 2016-11-09 | 2018-05-08 | Rec Silicon Inc | Reactor component placement inside liner wall |
| US10550731B2 (en) | 2017-01-13 | 2020-02-04 | LLT International (Ireland) Ltd. | Systems and methods for generating steam by creating shockwaves in a supersonic gaseous vortex |
| US10407310B2 (en) | 2017-01-26 | 2019-09-10 | Rec Silicon Inc | System for reducing agglomeration during annealing of flowable, finely divided solids |
| US20180208470A1 (en) * | 2017-01-26 | 2018-07-26 | Rec Silicon Inc | Method for annealing granular silicon with agglomeration control |
| US11203725B2 (en) | 2017-04-06 | 2021-12-21 | LLT International (Ireland) Ltd. | Systems and methods for gasification of carbonaceous materials |
| CN108821292B (en) * | 2017-05-05 | 2021-07-23 | 储晞 | Method and device for producing silicon monoxide |
| CN107601510B (en) * | 2017-09-21 | 2018-05-04 | 亚洲硅业（青海）有限公司 | A kind of device and method for preparing particle silicon seed |
| CN107745464A (en) * | 2017-10-25 | 2018-03-02 | 天津市万丰化工设备有限公司 | Gelatin particle production method |
| CN107715815A (en) * | 2017-11-01 | 2018-02-23 | 宁波工程学院 | A kind of granular polycrystalline silicon fluid bed process units of sound wave auxiliary |
| CN107792857B (en) * | 2017-11-28 | 2018-09-11 | 亚洲硅业（青海）有限公司 | A kind of production method and device of grain silicon |
| CN108002401B (en) * | 2017-12-27 | 2019-05-21 | 杨松 | It is a kind of to prepare kaolin production line |
| CN108083287B (en) * | 2017-12-27 | 2019-07-05 | 杨松 | It is a kind of to prepare kaolin production line application method |
| CN109487337A (en) * | 2018-11-02 | 2019-03-19 | 大连理工大学 | A kind of device and method of laser assisted purification Buddha's warrior attendant wire cutting silicon powder waste material |
| WO2020118482A1 (en) * | 2018-12-10 | 2020-06-18 | 储晞 | Reaction device for preparing particles and method for preparing particles |
| CN109607545A (en) * | 2019-01-02 | 2019-04-12 | 河南硅烷科技发展股份有限公司 | A kind of high purity silane CVD method continuously prepares the industrial method of nano silica fume |
| CN110182771B (en) * | 2019-06-10 | 2020-07-03 | 宁夏秦氏新材料有限公司 | Method for synthesizing silicon nitride by rotary kiln method |
| US10717061B1 (en) * | 2019-06-26 | 2020-07-21 | X Energy, Llc | Fluidized bed reactor system allowing particle sampling during an ongoing reaction |
| CN110355360B (en) * | 2019-07-10 | 2020-06-16 | 中国科学院过程工程研究所 | System and method for preparing zirconium coating layer |
| CN110850278A (en) * | 2019-09-04 | 2020-02-28 | 上海卓电电气有限公司 | Electromechanical integrated gas density relay |
| CN111888848B (en) * | 2020-09-03 | 2021-10-15 | 清华大学 | Coated particle preparation production line and gas-solid separation device thereof |
| CN113008622B (en) * | 2021-03-09 | 2022-07-26 | 亚洲硅业(青海)股份有限公司 | Particle silicon area melting detection sampling device |
| CN113275121A (en) * | 2021-06-11 | 2021-08-20 | 四川敏田科技发展有限公司 | High-purity quartz sand manufacturing system and manufacturing method |
| CN115385338A (en) * | 2022-08-01 | 2022-11-25 | 亚洲硅业(青海)股份有限公司 | Preparation method and device of silicon material |
| CN115212801B (en) * | 2022-08-30 | 2024-05-03 | 中国农业科学院草原研究所 | Compression molding device for crop straw pellet fuel processing |
| CN116036657B (en) * | 2023-03-16 | 2023-08-18 | 安徽瑞柏新材料有限公司 | Energy-saving separating equipment for butyl acetate production |
| CN117181138B (en) * | 2023-11-06 | 2024-03-26 | 上海氢田新材料科技有限公司 | Low-power-consumption high-efficiency high-adaptability gas heating device and heating method |
| CN117205848A (en) * | 2023-11-07 | 2023-12-12 | 上海氢田新材料科技有限公司 | System and method for preparing nano silicon based on gas phase decomposition method |
| CN117323920B (en) * | 2023-11-29 | 2024-01-26 | 山东金特安全科技有限公司 | Silicon carbide continuous flow reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786477A (en) * | 1985-12-28 | 1988-11-22 | Korea Research Institute Of Chemical Technology | Fluidized bed reactor with microwave heating system for preparing high-purity polycrystalline silicon |
| US4883687A (en) * | 1986-08-25 | 1989-11-28 | Ethyl Corporation | Fluid bed process for producing polysilicon |
| US5374413A (en) * | 1992-10-16 | 1994-12-20 | Korea Research Institute Of Chemical Technology | Heating of fluidized bed reactor by microwaves |
| CN101076493A (en) * | 2004-11-12 | 2007-11-21 | Memc电子材料有限公司 | High purity granular silicon and method of manufacturing the same |
Family Cites Families (127)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3020129A (en) * | 1958-07-25 | 1962-02-06 | Gen Electric | Production of silicon of improved purity |
| US3012861A (en) | 1960-01-15 | 1961-12-12 | Du Pont | Production of silicon |
| US3012862A (en) | 1960-08-16 | 1961-12-12 | Du Pont | Silicon production |
| US3647377A (en) * | 1968-08-29 | 1972-03-07 | Titan Gmbh | Process for the manufacture of fine particle size titanium dioxide by reacting titanium tetrachloride with oxygen |
| US3963838A (en) * | 1974-05-24 | 1976-06-15 | Texas Instruments Incorporated | Method of operating a quartz fluidized bed reactor for the production of silicon |
| US4154870A (en) * | 1974-11-01 | 1979-05-15 | Texas Instruments Incorporated | Silicon production and processing employing a fluidized bed |
| US3993450A (en) | 1975-02-19 | 1976-11-23 | The United States Of America As Represented By The United States Energy Research And Development Administration | Electrode assembly for a fluidized bed apparatus |
| US4207360A (en) * | 1975-10-31 | 1980-06-10 | Texas Instruments Incorporated | Silicon seed production process |
| US4084024A (en) * | 1975-11-10 | 1978-04-11 | J. C. Schumacher Co. | Process for the production of silicon of high purity |
| US4213937A (en) * | 1976-09-22 | 1980-07-22 | Texas Instruments Incorporated | Silicon refinery |
| US4298423A (en) | 1976-12-16 | 1981-11-03 | Semix Incorporated | Method of purifying silicon |
| US4289572A (en) * | 1976-12-27 | 1981-09-15 | Dow Corning Corporation | Method of closing silicon tubular bodies |
| US4170667A (en) * | 1977-01-31 | 1979-10-09 | Motorola, Inc. | Process for manufacturing pure polycrystalline silicon |
| DE2704975C2 (en) | 1977-02-07 | 1982-12-23 | Wacker-Chemie GmbH, 8000 München | Heat exchange device for fluidized bed reactors for carrying out gas / solid reactions, in particular for producing silicon-halogen compounds by means of silicon-containing contact masses |
| US4318942A (en) * | 1978-08-18 | 1982-03-09 | J. C. Schumacher Company | Process for producing polycrystalline silicon |
| US4676967A (en) * | 1978-08-23 | 1987-06-30 | Union Carbide Corporation | High purity silane and silicon production |
| US4292344A (en) * | 1979-02-23 | 1981-09-29 | Union Carbide Corporation | Fluidized bed heating process and apparatus |
| JPS55142538A (en) * | 1979-04-26 | 1980-11-07 | Mitsui Toatsu Chem Inc | Device used in reaction of vapor and solid |
| DE3016807A1 (en) * | 1980-05-02 | 1981-11-05 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | METHOD FOR PRODUCING SILICON |
| US4444811A (en) * | 1980-03-03 | 1984-04-24 | California Institute Of Technology | Fluidized bed silicon deposition from silane |
| US4314525A (en) * | 1980-03-03 | 1982-02-09 | California Institute Of Technology | Fluidized bed silicon deposition from silane |
| US4321246A (en) * | 1980-05-09 | 1982-03-23 | Motorola, Inc. | Polycrystalline silicon production |
| JPS57145021A (en) * | 1981-02-27 | 1982-09-07 | Shin Etsu Chem Co Ltd | Preparation of silicon granule |
| US4354987A (en) * | 1981-03-31 | 1982-10-19 | Union Carbide Corporation | Consolidation of high purity silicon powder |
| US4341749A (en) * | 1981-08-14 | 1982-07-27 | Union Carbide Corporation | Heating method for silane pyrolysis reactor |
| US4424199A (en) * | 1981-12-11 | 1984-01-03 | Union Carbide Corporation | Fluid jet seed particle generator for silane pyrolysis reactor |
| JPS58185426A (en) * | 1982-04-20 | 1983-10-29 | Hitachi Ltd | Preparation of high-purity silicon |
| US4668493A (en) * | 1982-06-22 | 1987-05-26 | Harry Levin | Process for making silicon |
| DE3223821A1 (en) * | 1982-06-25 | 1983-12-29 | Siemens AG, 1000 Berlin und 8000 München | METHOD AND DEVICE FOR PRODUCING HIGH PURITY SILICON GRANULES |
| FR2530607B1 (en) * | 1982-07-26 | 1985-06-28 | Rhone Poulenc Spec Chim | PURE SILICON, DENSE POWDER AND PROCESS FOR PREPARING SAME |
| US4642227A (en) * | 1982-08-20 | 1987-02-10 | California Institute Of Technology | Reactor for producing large particles of materials from gases |
| US4416913A (en) | 1982-09-28 | 1983-11-22 | Motorola, Inc. | Ascending differential silicon harvesting means and method |
| US4684513A (en) * | 1982-11-05 | 1987-08-04 | Union Carbide Corporation | Zone heating for fluidized bed silane pyrolysis |
| US4818495A (en) * | 1982-11-05 | 1989-04-04 | Union Carbide Corporation | Reactor for fluidized bed silane decomposition |
| JPS605013A (en) * | 1983-06-22 | 1985-01-11 | Denki Kagaku Kogyo Kk | Preparation of silicon powder and its device |
| JPS6077116A (en) * | 1983-09-30 | 1985-05-01 | Sumitomo Metal Ind Ltd | Production of silicon granule |
| US4806317A (en) * | 1985-08-01 | 1989-02-21 | Ethyl Corporation | Fluidized bed reactor |
| US5059410A (en) * | 1985-08-01 | 1991-10-22 | Ethyl Corporation | Production of silicon |
| US4691866A (en) * | 1985-11-08 | 1987-09-08 | Ethyl Corporation | Generation of seed particles |
| US4857173A (en) * | 1986-01-31 | 1989-08-15 | Ethyl Corporation | Particle classifier and method |
| US4820587A (en) * | 1986-08-25 | 1989-04-11 | Ethyl Corporation | Polysilicon produced by a fluid bed process |
| US4784840A (en) * | 1986-08-25 | 1988-11-15 | Ethyl Corporation | Polysilicon fluid bed process and product |
| US4748052A (en) * | 1987-08-21 | 1988-05-31 | Ethyl Corporation | Fluid bed reactor and process |
| US4868013A (en) * | 1987-08-21 | 1989-09-19 | Ethyl Corporation | Fluidized bed process |
| US4906441A (en) * | 1987-11-25 | 1990-03-06 | Union Carbide Chemicals And Plastics Company Inc. | Fluidized bed with heated liners and a method for its use |
| US4789596A (en) | 1987-11-27 | 1988-12-06 | Ethyl Corporation | Dopant coated bead-like silicon particles |
| US5139762A (en) * | 1987-12-14 | 1992-08-18 | Advanced Silicon Materials, Inc. | Fluidized bed for production of polycrystalline silicon |
| US4904452A (en) * | 1988-03-31 | 1990-02-27 | Union Carbide Chemicals And Plastics Company Inc. | Inner core heating in fluidized bed |
| DE3824065A1 (en) * | 1988-07-15 | 1990-01-18 | Bayer Ag | METHOD FOR PRODUCING SOLAR SILICON |
| US5242671A (en) * | 1988-10-11 | 1993-09-07 | Ethyl Corporation | Process for preparing polysilicon with diminished hydrogen content by using a fluidized bed with a two-step heating process |
| NO165288C (en) * | 1988-12-08 | 1991-01-23 | Elkem As | SILICONE POWDER AND PROCEDURE FOR THE PREPARATION OF SILICONE POWDER. |
| JPH02233514A (en) | 1989-03-06 | 1990-09-17 | Osaka Titanium Co Ltd | Production of polycrystalline silicon |
| JPH02279512A (en) | 1989-04-20 | 1990-11-15 | Osaka Titanium Co Ltd | Production of high-purity polycrystal silicon |
| US5165548A (en) | 1990-04-23 | 1992-11-24 | Hemlock Semiconductor Corporation | Rotary silicon screen |
| US5284676A (en) * | 1990-08-17 | 1994-02-08 | Carbon Implants, Inc. | Pyrolytic deposition in a fluidized bed |
| JPH04306354A (en) * | 1991-04-03 | 1992-10-29 | Hitachi Rubber Kako Kk | Soundproof support unit and double floor soundproof structure using the same |
| JPH05246786A (en) * | 1991-07-02 | 1993-09-24 | L'air Liquide | Method for uniformly coating core powders with ultrafine silicon-based particles while using chemical vapor decomposition in presence of core powders |
| JPH0680412A (en) * | 1992-08-31 | 1994-03-22 | Toagosei Chem Ind Co Ltd | Production of polycrystalline silicon |
| US5382412A (en) | 1992-10-16 | 1995-01-17 | Korea Research Institute Of Chemical Technology | Fluidized bed reactor heated by microwaves |
| JPH06127923A (en) * | 1992-10-16 | 1994-05-10 | Tonen Chem Corp | Fluidized bed reactor for producing polycrystalline silicon |
| JPH06127926A (en) * | 1992-10-20 | 1994-05-10 | Tonen Chem Corp | Production of granular polycrystalline silicon |
| JPH06127927A (en) * | 1992-10-20 | 1994-05-10 | Tonen Chem Corp | Production of granular polycrystalline silicon |
| JPH06191817A (en) * | 1992-12-22 | 1994-07-12 | Tonen Chem Corp | Production of granular polycrystal silicon |
| JPH08119787A (en) * | 1994-10-14 | 1996-05-14 | Komatsu Electron Metals Co Ltd | Dopant feeding method in continuously charging process and dopant composition |
| US6090360A (en) * | 1995-02-15 | 2000-07-18 | Dow Corning Corporation | Method for recovering particulate silicon from a by-product stream |
| DE69625688T2 (en) | 1995-06-07 | 2003-10-23 | Advanced Silicon Materials Llc, Moses Lake | METHOD AND DEVICE FOR DEPOSITING SILICON IN A FLUID BED REACTOR |
| US5798137A (en) * | 1995-06-07 | 1998-08-25 | Advanced Silicon Materials, Inc. | Method for silicon deposition |
| US5843234A (en) | 1996-05-10 | 1998-12-01 | Memc Electronic Materials, Inc. | Method and apparatus for aiming a barrel reactor nozzle |
| US5791493A (en) * | 1996-07-26 | 1998-08-11 | Memc Electronic Materials, Inc. | Polysilicon particle classifying apparatus |
| DE19735378A1 (en) | 1997-08-14 | 1999-02-18 | Wacker Chemie Gmbh | Process for the production of high-purity silicon granules |
| US6086678A (en) * | 1999-03-04 | 2000-07-11 | Memc Electronic Materials, Inc. | Pressure equalization system for chemical vapor deposition reactors |
| DE19948395A1 (en) | 1999-10-06 | 2001-05-03 | Wacker Chemie Gmbh | Fluidized bed reactor with radiative heating, useful for producing high purity polycrystalline silicon, e.g. for electronics, by passing silicon-containing gas over hot silicon particles |
| US6444027B1 (en) | 2000-05-08 | 2002-09-03 | Memc Electronic Materials, Inc. | Modified susceptor for use in chemical vapor deposition process |
| DE60142808D1 (en) * | 2000-05-11 | 2010-09-23 | Tokuyama Corp | Apparatus for producing polycrystalline silicon |
| JP4561944B2 (en) * | 2000-06-16 | 2010-10-13 | 株式会社サタケ | Granule sorter |
| US6455395B1 (en) * | 2000-06-30 | 2002-09-24 | Integrated Materials, Inc. | Method of fabricating silicon structures including fixtures for supporting wafers |
| US6450346B1 (en) * | 2000-06-30 | 2002-09-17 | Integrated Materials, Inc. | Silicon fixtures for supporting wafers during thermal processing |
| US6454851B1 (en) * | 2000-11-09 | 2002-09-24 | Memc Electronic Materials, Inc. | Method for preparing molten silicon melt from polycrystalline silicon charge |
| DE10057481A1 (en) * | 2000-11-20 | 2002-05-23 | Solarworld Ag | Production of high-purity granular silicon comprises decomposing a silicon-containing gas in a reactor made of carbon-fiber-reinforced silicon carbide |
| DE10060469A1 (en) * | 2000-12-06 | 2002-07-04 | Solarworld Ag | Process for the production of high-purity, granular silicon |
| DE10061682A1 (en) * | 2000-12-11 | 2002-07-04 | Solarworld Ag | Process for the production of high-purity silicon |
| DE10062419A1 (en) * | 2000-12-14 | 2002-08-01 | Solarworld Ag | Process for the production of high-purity, granular silicon |
| DE10063862A1 (en) * | 2000-12-21 | 2002-07-11 | Solarworld Ag | Process for the production of high-purity, granular silicon |
| US6827786B2 (en) * | 2000-12-26 | 2004-12-07 | Stephen M Lord | Machine for production of granular silicon |
| KR100411180B1 (en) * | 2001-01-03 | 2003-12-18 | 한국화학연구원 | Method for preparing polycrystalline silicon |
| DE10124848A1 (en) * | 2001-05-22 | 2002-11-28 | Solarworld Ag | Production of high-purity granular silicon by thermal decomposition of silanes or halosilanes in a fluidized-bed reactor comprises separating particles of the desired size in an external classifier |
| US7033561B2 (en) * | 2001-06-08 | 2006-04-25 | Dow Corning Corporation | Process for preparation of polycrystalline silicon |
| US6880263B2 (en) * | 2001-06-25 | 2005-04-19 | Jott Australia Pty Ltd. | Fluid/solid interaction apparatus |
| US6609870B2 (en) * | 2001-10-23 | 2003-08-26 | Memc Electronic Materials, Inc. | Granular semiconductor material transport system and process |
| WO2004013044A1 (en) * | 2002-07-22 | 2004-02-12 | Lord Stephen M | Methods for heating a fluidized bed silicon manufacture apparatus |
| NO20033207D0 (en) * | 2002-07-31 | 2003-07-15 | Per Kristian Egeberg | Process and reactor for the production of high purity silicon, and the use of the process and reactor in the production of high purity silicon from unrefined silicon |
| DE10243022A1 (en) * | 2002-09-17 | 2004-03-25 | Degussa Ag | Separation of a solid by thermal decomposition of a gaseous substance in a cup reactor |
| EP1666414A4 (en) * | 2003-08-22 | 2009-07-15 | Tokuyama Corp | Silicon manufacturing apparatus |
| DE10359587A1 (en) * | 2003-12-18 | 2005-07-14 | Wacker-Chemie Gmbh | Dust- and pore-free high-purity polysilicon granules |
| NO333319B1 (en) | 2003-12-29 | 2013-05-06 | Elkem As | Silicon material for the production of solar cells |
| DE102004010055A1 (en) | 2004-03-02 | 2005-09-22 | Degussa Ag | Process for the production of silicon |
| TWI255734B (en) * | 2004-03-30 | 2006-06-01 | Ind Tech Res Inst | Thermal regenerative granular-moving bed apparatus |
| JP2008506621A (en) | 2004-07-16 | 2008-03-06 | インスティチュート フォー エネルギーテックニック | Method and reactor for continuous production of semiconductor grade (SEG) silicon |
| WO2006016626A1 (en) * | 2004-08-11 | 2006-02-16 | Tokuyama Corporation | Silicon manufacturing apparatus |
| DE102004048948A1 (en) * | 2004-10-07 | 2006-04-20 | Wacker Chemie Ag | Apparatus and method for low-contamination, automatic breakage of silicon breakage |
| US7323047B2 (en) * | 2005-03-25 | 2008-01-29 | Kyocera Corporation | Method for manufacturing granular silicon crystal |
| US7790129B2 (en) * | 2005-07-29 | 2010-09-07 | Lord Ltd., Lp | Set of processes for removing impurities from a silcon production facility |
| US7622803B2 (en) * | 2005-08-30 | 2009-11-24 | Cree, Inc. | Heat sink assembly and related methods for semiconductor vacuum processing systems |
| DE102005041137A1 (en) * | 2005-08-30 | 2007-03-01 | Degussa Ag | Plasma reactor for cleaning silicon tetrachloride or germanium tetrachloride, comprises reactor housing, micro unit for plasma treatment, metallic heat exchanger, dielectric, perforated plate, lattice or network and high voltage electrode |
| KR100756310B1 (en) * | 2006-02-07 | 2007-09-07 | 한국화학연구원 | High-pressure Fluidized Bed Reactor for Preparing Granular Polycrystalline Silicon |
| KR100661284B1 (en) * | 2006-02-14 | 2006-12-27 | 한국화학연구원 | Preparation of granular polycrystalline using fluidized bed reactor |
| KR100813131B1 (en) | 2006-06-15 | 2008-03-17 | 한국화학연구원 | Method for sustainable preparation of polycrystalline silicon using fluidized bed reactor |
| US20080029020A1 (en) * | 2006-07-28 | 2008-02-07 | Kyocera Corporation | Method and apparatus for producing granular crystal |
| KR100783667B1 (en) * | 2006-08-10 | 2007-12-07 | 한국화학연구원 | Method and apparatus for preparation of granular polysilicon |
| US7935327B2 (en) | 2006-08-30 | 2011-05-03 | Hemlock Semiconductor Corporation | Silicon production with a fluidized bed reactor integrated into a siemens-type process |
| US20080128099A1 (en) * | 2006-12-05 | 2008-06-05 | Amrani Aviv Ltd. | Fabric for use as a lining material |
| DE102007021003A1 (en) | 2007-05-04 | 2008-11-06 | Wacker Chemie Ag | Process for the continuous production of polycrystalline high-purity silicon granules |
| US20080299015A1 (en) | 2007-06-04 | 2008-12-04 | Stephen Michael Lord | Apparatus and method for top removal of granular material from a fluidized bed deposition reactor |
| US7736614B2 (en) * | 2008-04-07 | 2010-06-15 | Lord Ltd., Lp | Process for removing aluminum and other metal chlorides from chlorosilanes |
| EP2310317A1 (en) | 2008-06-27 | 2011-04-20 | MEMC Electronic Materials, Inc. | Methods for increasing polycrystalline silicon reactor productivity by recycle of silicon fines |
| EP2303448B1 (en) | 2008-06-30 | 2012-10-31 | MEMC Electronic Materials, Inc. | Fluidized bed reactor systems and methods for reducing the deposition of silicon on reactor walls |
| US20100061912A1 (en) * | 2008-09-08 | 2010-03-11 | Stephen Michael Lord | Apparatus for high temperature hydrolysis of water reactive halosilanes and halides and process for making same |
| CN101676203B (en) | 2008-09-16 | 2015-06-10 | 储晞 | Reactor for producing high purity granular silicon and method thereof |
| US8178051B2 (en) * | 2008-11-05 | 2012-05-15 | Stephen Michael Lord | Apparatus and process for hydrogenation of a silicon tetrahalide and silicon to the trihalosilane |
| US7927984B2 (en) * | 2008-11-05 | 2011-04-19 | Hemlock Semiconductor Corporation | Silicon production with a fluidized bed reactor utilizing tetrachlorosilane to reduce wall deposition |
| US8168123B2 (en) | 2009-02-26 | 2012-05-01 | Siliken Chemicals, S.L. | Fluidized bed reactor for production of high purity silicon |
| CN102713001B (en) | 2009-11-18 | 2014-03-05 | 瑞科硅公司 | Fluid bed reactor |
| US8449848B2 (en) | 2010-10-22 | 2013-05-28 | Memc Electronic Materials, Inc. | Production of polycrystalline silicon in substantially closed-loop systems |
| US9156705B2 (en) | 2010-12-23 | 2015-10-13 | Sunedison, Inc. | Production of polycrystalline silicon by the thermal decomposition of dichlorosilane in a fluidized bed reactor |
| US8452547B2 (en) | 2010-12-29 | 2013-05-28 | Memc Electronic Materials, Inc. | Systems and methods for particle size determination and control in a fluidized bed reactor |
| NO20231208A1 (en) | 2011-09-30 | 2014-04-23 | Corner Star Ltd | Production of polycrystalline silicon by thermal decomposition of silane in a fluidized bed reactor |
| CN103842069B (en) | 2011-09-30 | 2016-10-05 | Memc电子材料有限公司 | Polysilicon is prepared by making silane thermally decompose in a fluidized bed reactor |
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2009
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- 2009-07-08 KR KR1020167034217A patent/KR101830856B1/en active IP Right Grant
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786477A (en) * | 1985-12-28 | 1988-11-22 | Korea Research Institute Of Chemical Technology | Fluidized bed reactor with microwave heating system for preparing high-purity polycrystalline silicon |
| US4883687A (en) * | 1986-08-25 | 1989-11-28 | Ethyl Corporation | Fluid bed process for producing polysilicon |
| US5374413A (en) * | 1992-10-16 | 1994-12-20 | Korea Research Institute Of Chemical Technology | Heating of fluidized bed reactor by microwaves |
| CN101076493A (en) * | 2004-11-12 | 2007-11-21 | Memc电子材料有限公司 | High purity granular silicon and method of manufacturing the same |
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| US9662625B2 (en) | 2017-05-30 |
| US8535614B2 (en) | 2013-09-17 |
| KR20110076930A (en) | 2011-07-06 |
| US20170361292A1 (en) | 2017-12-21 |
| EP2338835A1 (en) | 2011-06-29 |
| US20130337186A1 (en) | 2013-12-19 |
| CN103058194A (en) | 2013-04-24 |
| US9751066B2 (en) | 2017-09-05 |
| US20130336845A1 (en) | 2013-12-19 |
| KR101688442B1 (en) | 2016-12-21 |
| CN103058194B (en) | 2015-02-25 |
| KR20160144512A (en) | 2016-12-16 |
| KR20180019758A (en) | 2018-02-26 |
| CN101676203B (en) | 2015-06-10 |
| US10576438B2 (en) | 2020-03-03 |
| KR101830856B1 (en) | 2018-02-21 |
| US20110212011A1 (en) | 2011-09-01 |
| CN101676203A (en) | 2010-03-24 |
| CN103787336A (en) | 2014-05-14 |
| EP2338835A4 (en) | 2013-07-17 |
| WO2010031270A1 (en) | 2010-03-25 |
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